Solvent‐Gated Multimodal Charge Transfer Interactions for Precise Supramolecular Chirality Control

Abstract

ABSTRACT Despite the widespread application of charge transfer (CT) interactions in chiral optoelectronic materials, achieving multimodal CT interactions for the precise control poses significant challenges in both molecular design and practical implementation. Here, we develop amino acid‐based folded structures integrating pyrene donors and aryl imide acceptors with sterically hindering tert‐butyl groups, which exhibit dynamic through‐space CT interactions in solutions, enabled by reversible solvent‐gated folding/unfolding. The conformational switching induces distinct responses, enabling tunable emission spanning from blue to yellow to achieve white‐light emission, alongside precise regulation of chiroptical properties. Apart from solution‐based CT complexation, robust CT complexes with excellent chiroptical properties form within polymer matrices. Bottom‐up self‐assembly also leads to amplified chiroptical signals and the generation of macroscopic chirality. Remarkably, solvent ratio controls hierarchical self‐assembly via alternate or segregated CT stacking modes, generating helical aggregates with Inverted handedness, and simultaneously inducing macroscopic supramolecular chirality and enhanced chiroptical signals. Thermodynamically driven supramolecular chiral‐selective ripening inverts the initial kinetically trapped chirality, leveraging the stability of alternating CT stacks to achieve homochirality. This architecture exhibits remarkable solvent‐controlled modulation of luminescence, chiroptical handedness, and supramolecular chirality, offering a versatile platform for advanced photonics and multimodal encryption.